Barrierless On-Surface Metal Incorporation in Phthalocyanine-Based Molecules
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- Univ. of Chinese Academy of Sciences, Beijing (China). Inst. of Physics; Chinese Academy of Sciences (CAS), Beijing (China); Vanderbilt Univ., Nashville, TN (United States). Dept. of Physics and Astronomy & Dept. of Electrical Engineering and Computer Science
- Univ. of Chinese Academy of Sciences, Beijing (China). Inst. of Physics; Chinese Academy of Sciences (CAS), Beijing (China)
- Vanderbilt Univ., Nashville, TN (United States). Dept. of Physics and Astronomy & Dept. of Electrical Engineering and Computer Science; Univ. of Chinese Academy of Sciences, Beijing (China). Inst. of Physics; Chinese Academy of Sciences (CAS), Beijing (China)
On-surface metalation of metal-free phthalocyanine derivatives is a simple and solvent-free way to fabricate MPc compounds. Using phthalocyanine (H2Pc) molecules on Ag(111) as an example, we investigated the atomic-scale mechanisms of on-surface metalation processes using first-principles calculations based on density functional theory. When the molecules are deposited on a substrate first, we find that transition-metal atoms, except for Zn, drop directly from the vacuum into the molecule’s cavity without an energy barrier and bond with the inner four nitrogen atoms, with the two pyrrolic H atoms still in place. Subsequently, the two H atoms transfer to the substrate by overcoming small energy barriers and diffuse away. The substrate participates in the reaction by hybridization. In the alternative process, when metal atoms are adsorbed first on the surface and the H2Pc molecules are then added, the metal atoms diffuse into the cavity of the molecule via the molecule–surface interface by overcoming finite energy barriers. Finally, the above results provide insights into the on-surface metalation that can guide the control of the reaction pathway and products at the atomic level.
- Research Organization:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Vanderbilt Univ., Nashville, TN (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC); National Natural Science Foundation of China (NSFC)
- Grant/Contract Number:
- AC02-05CH11231; FG02-09ER46554
- OSTI ID:
- 1483798
- Alternate ID(s):
- OSTI ID: 1597885
- Journal Information:
- Journal of Physical Chemistry. C, Vol. 122, Issue 12; ISSN 1932-7447
- Publisher:
- American Chemical SocietyCopyright Statement
- Country of Publication:
- United States
- Language:
- English
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